WO2005073327A1 - Plate printing ink, spacer and display device - Google Patents

Abstract

An ink for spacer formation for use in plate printing process, in which the influence of binder on the physical properties of spacer is inhibited. There is provided an ink for spacer formation for use in plate printing process, comprising spacer particles and a thermosetting resin composition for spacer particle dispersion, characterized in that the thermosetting resin composition contains a component having polycaprolactone structure.

Description

 Specification

 Technical Field of the Invention The invention relates to plate-type printing inks, spacers and display devices.

 The present invention relates to a printing ink, a spacer, and a display device.

 Background art

 Japanese Patent Application Laid-Open No. 2000-35582 discloses a spacer forming method by gravure offset printing. In claims 2 and 3 of JP-A-2000-35582, use is made of an ink obtained by blending 20 to 60% by weight of a spherical spacer in a resin having a viscosity of 2000 to 2500 cps. In the working examples, a resin spacer beads of 5% and a polyester-based resin are shown.

 Japanese Patent Application Laid-Open Nos. Hei 11-32-23020, Hei 9-1111170, and Hei 7-11404 disclose color filter layers by intaglio offset printing. It is described that polyester-melamine resin, epoxy melamine resin and the like are used as heat-curable inks suitable for forming black matrix. Disclosure of the invention

In JP-A-2000-35582, only the viscosity is specified for the resin. In the examples, a polyester resin is shown, and only the particle size of the resin spacer beads is defined. However, with this spacer, it was found that the physical properties of the ink when actually printed were often affected by the binder resin, resulting in physical properties different from those of the spherical spacer itself. In particular, such as the breaking strength of the spacer, the 10% compressive strength, the compressibility, and the recovery rate 2005/001558

2

Physical properties fluctuated greatly compared to the physical properties of the spherical spacer. An object of the present invention is to suppress the influence of a binder on physical properties of a spacer in a spacer forming ink used in a plate printing method.

 The present invention relates to a spacer forming ink used in a plate printing method, comprising a spacer particle, and a thermosetting resin composition in which the spacer particle is dispersed. The conductive resin composition comprises a component having a polyprolactone structure.

 In addition, the present invention relates to a method for forming a spacer, comprising forming a spacer by printing the plate printing ink on a substrate, heat-treating and curing the ink. is there. Further, the present invention relates to a spacer characterized by being formed by this method, and to a display device comprising the spacer. It is.

 By printing and thermally curing the printing ink of the present invention, it is possible to suppress the influence of the binder resin and to form a spacer having the same or substantially the same physical properties as the spherical spacer itself. it can. For example, in the liquid crystal display device schematically shown in FIG. 1, a spherical spacer particle 2 is interposed between a pair of substrates 4, and the liquid crystal 1 is filled between the pair of substrates 4. On the other hand, in the case of the present invention, as schematically shown in FIG. 2, the spacer particles 2 are formed on the surface of the substrate by the cured product 3 of the thermosetting resin composition constituting the ink. Stick. According to the present invention, even when the spacer particles 2 are fixed to the surface of the substrate 4 with the resin 3, the same physical characteristics as those of the spacer particles 2 alone in FIG. 1 can be obtained. .

Brief Description of Drawings FIG. 1 is a partial cross-sectional view schematically showing one example of a liquid crystal display device obtained by a conventional method.

 FIG. 2 is a partial cross-sectional view schematically showing one example of a liquid crystal display device obtained by using the printing ink of the present invention.

 Figure 3 is a test car displacement graph showing the results of a compression test using a spherical spacer alone.

 FIG. 4 is a test car displacement graph showing a compression test result in Example 1.

 FIG. 5 is a test car displacement graph showing a compression test result in Comparative Example 1.

 FIG. 6 is a test force-displacement graph showing the results of a load-unload test using a spherical spacer alone.

 FIG. 7 is a test car displacement graph showing the results of the load-unload test in Example 1.

 FIG. 8 is a test car displacement graph showing the results of the load-unload test in Comparative Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

 The plate printing ink of the present invention comprises a spacer particle and a thermosetting resin composition for dispersing the spacer particle, wherein the thermosetting resin composition has a component having a polyprolactone structure. including. It also contains solvents, viscosity modifiers and other additives as needed. Each of these elements will be described in turn.

 (Plate printing method)

This means a printing method using a plate, and the following methods can be exemplified. It does not include non-printing systems such as the inkjet system and laser system. (1) Letterpress printing (direct printing method, offset method)

 (2) Intaglio printing or gravure printing (transfer method, offset method, pad method)

 (3) Lithographic printing or offset printing

 (4) Stencil printing or screen printing

 [Spacer particles]

 The material of the spacer particles is not particularly limited, and examples thereof include a resin, an organic substance, an inorganic substance, a compound and a mixture thereof. The above resin is not particularly limited, and examples thereof include polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamide, and polyimide. Linear or cross-linked polymers such as polysulfone, polyphenylene oxide and polyacetal; epoxy resins, phenolic resins, melamine resins, benzoguanamine resins, unsaturated polyester resins, divielbenzene polymers, divinylbenzene

Resins such as -styrene copolymer, divinylbenzene-acrylic acid ester copolymer, diaryl phthalate polymer, and triaryl isocyanurate polymer, etc. Preferably, the composite particles are selected as spacers. Further, the coating material of the spacer is not particularly limited, and examples thereof include a resin and a low melting point metal. The above resin is not particularly limited, and examples thereof include polyolefins such as polyethylene, ethylene / vinyl acetate copolymer, and ethylene acrylate copolymer; polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl. (Meth) acrylate polymers or copolymers such as (meth) acrylate; polystyrene, styrene / acrylic acid ester copolymer, SB type styrene / butadiene Lock copolymers, SBS-type styrene / butadiene block copolymers, block polymers such as these water additives; thermoplastic resins such as vinyl polymers or copolymers, epoxy resins, phenolic resins, melamine resins, etc. Thermosetting resins, mixtures thereof, etc. are preferred, but it is preferred that they are not simply physically bonded but chemically bonded.

 In a preferred embodiment, in the spacer particle, the particle surface and the polymer constituting the adhesion layer are bound by a covalent bond. Examples of the method include a graft polymerization method and a polymer reaction method. In the graft polymerization method, a polymerizable vinyl group is introduced into the particle surface, and the monomer is polymerized starting from the vinyl group.A polymerization initiator is introduced into the particle surface, and Two methods of polymerizing the monomer are considered. The thermosetting resin composition of the present invention contains at least a component having a polyprolactone structure. The composition includes at least two components that can be cured by heat treatment, one of which includes a polyprolactone structure. Preferably, the so-called base resin contains a polyprolactone structure, and the resin is reacted with a curing agent for causing a crosslinking reaction.

 [Thermosetting resin containing polyprolactone structure]

 Examples of the thermosetting resin having a polyprolactone structure include a polyester resin, an acrylic resin, an epoxy resin, and a reaction product of a polyester resin having a polyprolactone structure and an acid anhydride.

 (Polyester resin with polyprolactone structure)

Examples of the polyester resin having a polyprolactone structure include polyprolactone polyol alone or two or more types. Examples of the polyprolactone polyol include those described in (0116) of JP-A-11-228905. This poly force prolactone poly As an oar, for example,

m+nは 4〜35の整数

m + n is an integer from 4 to 35

Gく ΓΙウノ。 (し

G-kun. (S

Bifunctional polycaprolactones such as

1 + m + n is an integer from 3 to 30

_{R: CH 2 GHGH 2, CH} 3 C (CH 2) 3, CH 3 CH 2 C (CH 2) 3 functional poly force Puroraku Tonto triol, such as _3, the use of tetrafunctional Porikaburora click Tonporio Ichiru etc. Can be. .

Polyols that have not been modified with polyalkylprolactone, such as polyethylene glycol, polypropylene glycol, polycarbonate diol, and polyester polyol, with respect to the polyalkylprolactone polyol. 05 001558

7

Can be used together. In addition, polycondensation products of polycaprolactone polyol with the following dicarboxylic acids and polyols can be mentioned.

 Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, and the like, and lower alkyl esters and acid anhydrides thereof. These may be used alone or in combination of two or more. it can.

 Examples of the fatty acid dicarboxylic acid component include adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, hymic acid, and the like, and lower alkyl esters and acid anhydrides thereof. Or two or more types can be used.

 The diol components include, as dialcohols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentenediol, 1,6-hexanediol diethylene glycol, neopentyl alcohol, 1,4-cyclohexane dimethanol, 3-methylpentane-1,5-diol, 1,4-dicyclohexane methanol, xylylene glycol, Examples thereof include aliphatic or aromatic dialcohols such as ethylene oxide or propylene oxide adduct of bisphenol A and hydrogenated bisphenol A. These may be used alone or in combination of two or more.

 Examples of trihydric or higher alcohols include trimethyi monoluethane, trimethylolpropane, glycerin, penju erythritol and the like, and these can be used alone or in combination of two or more.

 Using these raw materials, a polyester resin having a polyprolactone structure can be obtained by a known polycondensation method (Reference: Introduction to paint synthesis resin, Kyozo Kitaoka, Shin Kobun Bunko 7 Polymer Publishing Association).

(Acrylic resin with polyprolactone structure) 5 001558

 8

 An acrylyl resin having a polyprolactone structure can be obtained by radical polymerization of (meth) acrylate having a polyprolactone structure (and other vinyl monomers as necessary).

 As the polyprolactone-modified hydroxyxethyl (meth) acrylate, a compound represented by the following general formula can be exemplified.

R

CH -CCOCH ₂ CH O- [G (CH ₂ ) ₅ 0¾- H

 II II

0 0 R: H or CH ₃

 n: "!! An integer from 25

Specifically, polycaprolactone-modified hydroxethyl (methyx) acrylate (“Braxel FM”, “Braxel FA” (Daicel Chemical)), lipoxyl-terminal flexible (meth) acrylate (“Braxel FMA (Dicel Chemistry)), acetoacetyl group terminal flexible (meth) acrylate (“Placcel FD” (Daicel Chemical)), and the like. Other vinyl monomers that can be used in combination include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, and tetrahydrofurfuryl. Acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, methyl vinyl ether , N-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrene, — Methylstyrene, acrylonitrile, methyl acrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, aryl glycidyl ether, acrylic Acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, acrylamide, methyl acrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, N N, N-dimethylaminoethyl methacrylate, N, N-getylaminoethyl methacrylate, diacetone acrylamide and the like. Further, vinyl monomers having an OH group such as 2-hydroxylethyl acrylate, 2-hydroxylethylmethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and aryl alcohol may be used. It can also be used. In addition, a reaction product of Ryzydula E with acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, or the like can also be used. The above examples do not limit the present invention.

 Using these raw materials, an acrylic resin having a polyproprolactone structure can be obtained by a known radical polymerization method (Reference: Introduction to paint synthesis, resin by Kyozo Kitaoka, Shin Kobunko Bunko 7 Polymer Publishing Association). A commercially available acrylic resin having a polyprolactone structure is "Braxel DC" series.

 [Polyester resin with polylactone structure

 Acid anhydride reactant]

 The reaction product can be easily synthesized by reacting various acid anhydrides with the O H group of the polyester resin having a polyprolactone structure exemplified above.

The acid anhydrides that can be used here include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid. T / JP2005 / 001558

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Aqueous products, aromatic carboxylic acid anhydrides such as ethylene glycol trimeric anhydride, biphenyltetracarboxylic acid anhydride, and aliphatic carboxylic acid anhydrides such as azelaic acid, sebacic acid, and dodecane diacid And alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, acetic anhydride, and hymic anhydride.

 (Epoxy resin with polyprolactone structure)

Examples of epoxy resins having a polyprolactone structure include lactone-modifying epoxy resins (for example, “Braccel G” series), flexible alicyclic epoxy resins (for example, “Celoxide 280” series), And polyfunctional alicyclic epoxy resins (“Evolid GT300” and “Evolid GT400”). These can be used alone or in combination of two or more. It can be used in combination with a resin. Specific examples of such epoxy compounds that can be used in combination include, for example, hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, phenyl diglycidyl ether, phenol novolak epoxy resin, and cresol novolak. Epoxy resin, Trishydroxyphenyl methane epoxy resin, Dicyclobenzene epoxy resin, Bisphenol-A epoxy resin, Bisphenol-F epoxy resin, Bisphenol-S epoxy resin Resin, 2,2-bis (4-hydroxyphenyl) 1-1,1,1,1,3,3,3-hexafluoropropane epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bis Phenol-F-type epoxy resin, hydrogenated bisphenol-S-type Epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) — 1,1,1,1,3,3,3-hexafluoropropane epoxy compound, brominated bisphenol-A epoxy resin , Brominated JP2005 / 001558

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Sulfonol-F epoxy resin, silicone D hexane dimethanol diglycidyl ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, polysulfide diglycidyl Examples include ethers, biphenol-type epoxy resins, bisphenol-A novolak-type epoxy resins, epoxy resins containing a naphthalene skeleton, and heterocyclic epoxy resins.

 (Other resin with polyforce prolactone structure)

 In addition, lactone-modified phenoxy resin, lactone-modified butyral, and the like can also be used as resins that can be used in the present invention.

 [Curing agent]

 The curing system for imparting thermosetting properties to the thermosetting resin composition is not particularly limited. For example, a melamine resin can be blended, and a curing agent and an acid catalyst can be added. Examples of such a curing agent include an acid anhydride, an amine curing agent, and a cationic curing agent.

 In the present invention, in the step of disposing the spacer under the alignment film, the spacer needs to have heat resistance. Therefore, the following combinations are particularly preferable from the viewpoint of the heat resistance of the spacer.

 Polyester resin and melamine resin with polyprolactone structure

 (Example 1) Acrylic resin and melamine resin having a polyprolactone structure (Example 3)

 Polyester resin and epoxy resin with polyprolactone structure Acryl resin and epoxy resin with polyprolactone structure Reaction product of polyprolactone polyol and acid anhydride and epoxy resin

(Example 2) In particular, in the case of a combination of a polyester resin having a polyprolactone structure and a melamine resin, in order to improve thermosetting properties, some of the OH groups of the polyester polyol having a polyprolactone structure are used as an acid anhydride. To introduce a COOH group or co-condensate the polyester resin and the melamine resin in advance.

 In the case of an acrylic resin, it can be introduced by using a monomer having a COOH group of a vinyl monomer, such as methylacrylic acid or acrylic acid.

 (Melamine resin)

 The melamine resin used in the present invention is a compound in which melamine is made to act on formaldehyde, or an alkyl-modified compound of this compound. Specific examples of such melamine resins include “Nicolor MS-21, MS-11, MW-24, MS-001, MX-002, MX- 730, MX-750, MX-708, MX-706, MX-042, MX-410, Mitsui Cytec Co., Ltd.'s Cymel 370, 771, 3 2 5, 327, 703, 712, 715, 701, 202, 207j, etc. These melamine resins may be used alone or in combination of two or more. can do.

Specific examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromeric anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol trimellitic anhydride. Anhydrides, aromatic carboxylic anhydrides such as biphenyletracarboxylic anhydride, aliphatic carboxylic anhydrides such as azelaic acid, sebacic acid, and dodecane diacid, tetrahydrophthalic anhydride, hexahydrophthalic acid Alicyclic carboxylic anhydrides such as anhydrides, nadic anhydrides, wet anhydrides, and high anhydrides are exemplified. Specific examples of the amine curing agent include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diamino. Aromatic amines such as naphthalene, m-xylylenediamine, ethylenediamine, ethylenediamine, isophoronediamine, aliphatic amines such as bis- (4-amino-3-methyldicyclohexyl) methane, polyetherdiamine, dicyandiamine And guanidines such as 1- (o-tolyl) biguanide.

 Typical catalysts include tertiary amines (tris (dimethylaminomethyl) phenol, dimethylbenzylamine, 1,8-diazabicyclo (5,4,0) indene (DBU)), imidazoles, etc. It is.

 As the acid catalyst, acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, butylphosphoric acid, and octylphosphoric acid, and amine-neutralized products of these acids are preferable. .

 The lithographic printing ink of the present invention may contain a solvent.

 Examples of the solvent include the following.

 (1) Low boiling solvent with boiling point of 120 ° C or less

 Aliphatic hydrocarbons such as n-hexane, n-heptane and rubber volatile oil; aromatic hydrocarbons such as hexane, toluene, and methylcyclohexane; methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropanol Alcohols such as pill alcohol, n-butyl alcohol, secondary butyl alcohol, and isobutyl alcohol; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and n-propyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl ketone Ketones.

(2) Medium boiling solvent with boiling point of 120 to 230 ° C PT / JP2005 / 001558

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 Aliphatic hydrocarbons such as mineral spirits 1, etc .; Aromatic hydrocarbons such as xylene, solvent naphthene, tetralin, dipentene; alcohols such as cyclohexyl alcohol, 2-methylcyclohexyl alcohol; esters such as butyl acetate; Cyclohexanone, methylcyclohexanone, diacetone alcohol, ketones such as isophorone, glycols such as ethylene glycol and propylene glycol; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Glycol ethers such as butyl ether; ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Glycol ether esters such as rumonoethyl ether acetate

 (3) High boiling solvent with boiling point of 230 to 320 ° C

 Aliphatic hydrocarbons such as ink oil; alcohols such as tridecyl alcohol; glycols such as methylene glycol, triethylene glycol and dipropylene glycol; glycol ethers such as diethylene glycol monobutyl ether; glycols such as methylene glycol monobutyl ether acetate. Examples of such a solvent are described in Table 2.8 on page 43 of "Introduction to Printing Ink" (by Jiro Aihara, Printing Society of Japan).

The plate-type printing ink of the present invention can be used to form a spacer on a glass substrate for a liquid crystal panel by a printing method disclosed in JP-A-2000-35582. From the viewpoints of suitability for the silicone blanket used in this printing method and printing accuracy, alcohols having 9 or more carbon atoms (for example, “Dianal” manufactured by Mitsubishi Chemical Corporation) were used as solvents. Aliphatic hydrocarbon solvent of 0 ° C or higher, aromatic hydrocarbon solvent of boiling point of 120 ° C or higher, 2005/001558

Fifteen

Glycol ethers and glycol ether esters are preferred (see Reference: Introduction to printing inks, supplemented by Jiro Aihara, Printing Society Press).

 In the ink of the present invention, a viscosity modifier may be used to adjust the ink viscosity to a level suitable for printing. Examples of viscosity modifiers include ultrafine silica (for example, AEROSIL manufactured by Nippon Aerosil Co., Ltd., MIZURICHI SIL manufactured by Mizusawa Chemical Co., Ltd., SILICA, Silo Hobik, FUSOKA manufactured by Fuji Silica Chemical Co., Ltd.) Chemical Industry Co., Ltd., trade name, etc.).

 The spacer formed by the printing ink and plate printing in this manner has almost the same physical strength as the spherical spacer alone, such as the breaking strength, 10% compression strength, and compression ratio of the spacer. Further, the adhesiveness can be imparted while maintaining the characteristic properties.

 The present invention can be achieved by including, as a binder resin that does not suppress the physical properties of the spherical spacer, a component having a polyprolactone structure, but further from the viewpoint of the physical properties of the binder resin. It can be seen that the Young's modulus is 0.1 to 9.0 GPa (more preferably, 0.2 to 5.0 OGPa) and the restoration rate is 60% or more (more preferably, 70% or more to 100%). Desirably.

 Within this range, the binder resin has sufficient flexibility and resilience to the spherical spacer, so that the spherical spacer alone has almost the same breaking strength, compression ratio, A spacer having a% compressive strength can be formed by printing.

However, when the Young's modulus of the ink resin exceeds 9.0 GPa or the restoration rate is less than 60%, the binder resin is harder than the spacer particles and harder to deform. The spacer formed by the process is also hard to be deformed under the influence of the binder resin, and the resilience is also reduced. I will. Therefore, the spacer formed by printing has a higher breaking strength, a lower compression ratio, and a higher 10% compression strength than the spherical spacer alone. In this case, when bonding the LCD substrate by the liquid crystal dropping method, if the amount of the liquid crystal dropped is small, the spacer is not deformed, and residual bubbles are easily generated. In addition, when the environment in which the LCD is used is low temperature, the internal liquid crystal contracts in volume, and if the spacer does not deform due to external pressure applied at that time, low-temperature foaming is likely to occur.

 If the Young's modulus is smaller than 0.01 GPa, the physical properties of the spacer formed by printing may be close to those of the spherical spacer alone. However, since the adhesion is insufficient, the spacer is likely to fall off the substrate in the subsequent cleaning step, rubbing step, and the like, and when the LCD substrate is bonded, gap unevenness occurs in the display section. On the other hand, since the cross-linking structure is not sufficient, the coating liquid for the alignment film permeates into the printed spacer at the time of printing, so that the alignment film cannot be formed around the spacer and causes poor alignment of the liquid crystal. Example

 (Example 1 (polyester resin + melamine resin))

"Placcel 410 Dj (Polycaprolactone tetraol, manufactured by Daicel Chemical Industries, Ltd.) 45 parts by weight, carboxylic acid-containing polycaprolactone triol (polycaprolactone triol and tetrahydrofuranic anhydride 1: 1 molar ratio adduct) 20 parts by weight, "Cymer 303" (melamine resin, Mitsui Cytec Co., Ltd.) 35 parts by weight, "Dianal 135" (solvent: 13 to 13 carbon atoms) 15 parts by weight of a higher alcohol mixture (manufactured by Mitsubishi Chemical Corporation) were mixed and reacted at 120 to 125 ° C for 6 to 7 hours. Further, 100 parts by weight of the above resin liquid (total amount), “Aerosil 300 CF” (viscosity control) PT / JP2005 / 001558

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Preparative agent: porous silica, manufactured by Nippon Aerosil Co., Ltd.) 12 parts by weight, 25 parts by weight of "Dianal 135" (the solvent) are premixed and dispersed by a roll to obtain a resin composition for ink. Was.

The obtained resin composition was applied to a glass plate using “Doc Yuichi 4 MIL” and cured at 220 ° C. for 1 hour to form a film. The film had a Young's modulus of 0.56 GPa (universal hardness of 22.4 N / mm ² ) and a recovery rate of 90%. The method of measuring the restoration rate is as follows.

Huitsuya Corporation Co., Ltd.

Film thickness 20〃m or more (on glass plate)

Indenter used

Maximum load 1 OmN

Load speed 10mN / 8sec

Creep time at maximum load 60 sec

Unloading speed 10mN / 8 sec

Creep time at minimum load 60 sec

 On the other hand, particle size 4 zm, breaking strength 774 MPa, 10% compressive strength 52 M

A spherical particle having a Pa, a compression ratio of 33.2%, and a recovery ratio of 18.9% (measurement apparatus: micro compression tester MC TM-201, Shimadzu Corporation) was prepared. The test conditions are as follows. Fig. 3 is a test force-displacement graph showing the results of the compression test, and Fig. 6 is a test force-displacement graph showing the results of the load-unloading test.

Shimadzu Corporation Micro compression tester MCTM-20 1

Indenter used FLAT 50

Compression test (Fig. 3)

Load speed 0.88 mN / sec Load-unloading test (Fig. 6)

Maximum load 9.8 mN

Load speed 0.2 8 mN / s Θ c

Retention time 0 sec

Minimum load 0.98 mN

 65 parts by weight of the spacer particles were dispersed in a mixer by 35 parts by weight of “Dianal 1 35” to prepare a spacer dispersion. 100 parts by weight of the above resin composition for ink and 65 parts by weight of the above spacer dispersion were blended and dispersed by a mixer to prepare a printing ink (a spacer content of 25%). ). The printing was performed by printing on a glass substrate according to the method described in JP-A-2000-35582 and curing at 220 ° C. for 1 hour. The breaking strength of the spacer formed on the glass substrate was 756 MPa, the 10% compressive strength was 60.3 MPa, the compression ratio was 32.3%, and the spacer was The physical properties were almost the same as those of the particles alone. Fig. 4 is a test force-displacement graph showing the results of the compression test, and Fig. 7 is a test force-displacement graph showing the results of the load-unloading test. Patterns similar to the graphs in Figs. 3 and 6, respectively, were shown.

 (Comparative Example 1)

 170 parts by weight of trimellitic anhydride, 16 parts by weight of hydrofluoric anhydride, 16 parts by weight of adipic acid, 270 parts by weight of neopentyl glycol and 40 parts by weight of methyl isobutyl ketone were placed in a reaction vessel. 0 ° C; 140 ° 180 ° C for 1 hour each, and 220 ° C for 2 hours for dehydration condensation to obtain a polyester resin. This resin is combined with “Cymer 303” (melamine resin, Mitsui Cytec 2 40 parts by weight were blended, and an ink resin and a printing ink were prepared in the same manner as in Example 1.

The Young's modulus of the printing ink resin was 9.4 GPa (universal hardness 391 N / mm ² ), and the restoration rate was 60%. TJP2005 / 001558

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 The physical properties of the spacer formed on the glass substrate were as follows: breaking strength was 210 MPa, 10% compressive strength was 101.5 MPa, and compressibility was 26.1%. Due to the ink resin, the physical properties were different from those of the spacer particles alone. Fig. 5 is a test force-displacement graph showing the results of the compression test, and Fig. 8 is a test car displacement graph showing the results of the load-unloading test. Each pattern showed a different pattern from the graphs in Figs.

 (Comparative Example 2)

 65 parts by weight of Byron 220 (polyester resin, Toyobo Co., Ltd.), 35 parts by weight of Cymel 303, and 25 parts by weight of propylene glycol monoethyl acetate Thereafter, in the same manner as in Example 1, an ink resin and a printing ink were prepared. The Young's modulus of the printing ink resin was 10.6 9 GPa (universal hardness: 34 N / mm) ヽ The restoration rate was 44%.

 The breaking strength of the spacer formed on the glass substrate is 2297MPa, 10% compressive strength 93.6MPa, the compression ratio is 25.9%, and it depends on the ink resin used. The physical property values were different from those of the sphere particles alone.

 (Example 2 (epoxy resin))

 33 parts by weight of “Placcel 410D” and 50 parts by weight of methyltetrahydrofluoric anhydride were reacted at 90 ° C. for 5 hours to obtain a reaction product whose terminal was COOH-grouped. 40 parts by weight of this reaction product, 35 parts by weight of "Eporide GT302" (lactone-modified epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) and 25 parts by weight of "propylene glycol monoethyl ether acetate" (solvent) Merged. Hereinafter, an ink resin and a printing ink were prepared in the same manner as in Example 1. The Young's modulus of the printing ink resin was 0 · 58 GPa (universal hardness 23.8 N / mm), and the restoration rate was 88.2%.

Breakdown strength of the sensor formed on the glass substrate 771.9MPa, PT / JP2005 / 001558

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 At 10% compressive strength of 65.1 MPa and a compressibility of 32.8%, the same physical property values as those of the spacer particles alone were exhibited depending on the ink resin used.

 (Example 3 (acrylic resin + melamine resin))

 75 parts by weight of “propylene glycol monoethyl acetate”, 75 parts by weight of “Braxel FA-5” (lactone modified acrylate, Daicel Chemical Industries, Ltd.), 57 parts by weight of MMA (methyl methyl acrylate), HE MA (Hexaethyl methacrylate) 15 parts by weight, MA A (methacrylic acid) 3 parts by weight, "ABN-E" (azo polymerization initiator, Nippon Hydrazine Industry Co., Ltd.) 3 parts by weight 80-90 ° C. for 5 hours, 25 parts by weight of "Suzul 1500" and 0.3 part by weight of "ABN-E" were added and polymerized for 3 hours to obtain a resin having a solid content of 60%. To this resin, 75 parts by weight of “CYMEL 303” was blended, and a resin for ink and a printing ink were prepared in the same manner as in Example 1.

The Young's modulus of the printing ink resin was 3.36 GPa (universal hardness: 19.3 N / mm ² ), and the restoration rate was 75%.

 Breaking strength of the sensor formed on the glass substrate 97 1.7MPa, 10% compressive strength 68.3MPa, compressibility 30.0%, depending on the ink resin used. It showed the same physical properties.

 (Example 4 (polyester resin + melamine resin))

The procedure was performed in the same manner as in Example 1 except that "Blaccel 410D" was replaced with "Placcel 303" (Polycaprolactone Triol, manufactured by Daicel Chemical Industries, Ltd.). The resulting film had physical properties of Young's modulus of 3.05 (universal hardness of 79.7 N / mm ² ) and recovery of 65.7%. The breaking strength of the spacer formed on the glass substrate was 882 MPa, 10% compressive strength 68.8 MPa, and compressibility 29.7%.

(Example 5 (polyester resin + melamine resin)) T / JP2005 / 001558

twenty one

The same procedure was performed as in Example 1 except that "Placcel 410D" was replaced by "Placcel 308" (Polycaprolactone Triol, manufactured by Daicel Chemical Industries, Ltd.). The physical properties of the obtained film were as follows: a Young's modulus of 0.21 (universal hardness 9.5 NZmm ² ) and a restoration rate of 88.5%. The breaking strength of the spacer formed on the glass substrate was 740.2 MPa, 10% compressive strength 52.8 MPa, and compressibility 35.1%. Was.

 [Comparative Example 3]

80 parts by weight of “PTMG 2000” (polytetramethylene glycol, Mitsubishi Chemical Corporation), 20 parts by weight of “CYMER 303”, and 10 parts by weight of “Dialal 135” Thereafter, a resin for ink and a printing ink were prepared in the same manner as in Example 1. The Young's modulus of the printing ink resin was 0.08 GPa (universal hardness: 4.9 NZmm ² ) and the restoration rate was 92.4%. The breaking strength of the spacer formed on the glass substrate was 763 MPa, 10% compressive strength 53.5 MPa, and compressibility 34.5%.

 Tables 1 and 2 show the experimental results of the examples and comparative examples. In Tables 1 and 2, the adhesion and solvent resistance were measured as follows.

 Adhesion: Printed and dried on an IT0 substrate in the same manner as in Example 1 to prepare a test piece, a cellophane tape peeling test was performed, and the remaining rate of the spacer before and after the test was evaluated.

 "〇": 100%

 "Mouth": 95-: L 0 0%

 "X": 95% or less

 Solvent resistance: A spot test was performed on a film obtained in the same manner as in the film preparation method in Example 1 using NMP as a solvent, and the appearance after the test was visually observed.

"〇": No change in appearance "Mouth": Spot marks remain

 "X": Swell or dissolve

Table 1 Physical properties Example 1 Example 2 Example 3 Example 4 Example 5 By-Young's modulus 0.56 0.5 0.5 8 3.3 6 3.0 0.5 0.21

 Restoration rate (%) 9 0 8 8. 2 7 5 7 8. 5 8 8.5 Surge strength 7 5 6 771.9 971.7 8 82 740.2 ぺ (M Pa)

 10% compression 60.3 6 5.1 6 8.3 68.8 52.8 strength

 (MP a)

Compressibility (%) 3 2. 3 3 2. 8 3 0.0 2 9. 7 3 5. 1 Adhesion 〇 〇 〇 □ □ Solvent resistance 〇 〇 〇 〇 〇 Table 2

本発明の特定の実施形態を説明してきたけれども、 本発明はこれら 定の実施形態に限定されるものではなく、 請求の範囲の範囲から離れ ことなく、 種々の変更や改変を行いながら実施できる。

Although specific embodiments of the present invention have been described, the present invention is not limited to these specific embodiments, and can be implemented with various changes and modifications without departing from the scope of the claims.

Claims

The scope of the claims  1. An ink for forming a spacer used in a plate printing method,  Comprising a spacer particle, and a thermosetting resin composition for dispersing the spacer particle, wherein the thermosetting resin composition comprises a component having a polyforce prolactone structure, Plate printing ink.  2. The ink for lithographic printing according to claim 1, characterized in that it contains one or more solvents selected from the group consisting of higher alcohols, aliphatic hydrocarbons and aromatic hydrocarbons.  3. The plate printing ink of claim 1 or 2, further comprising a viscosity modifier comprising porous silica.  4. A spacer is formed by printing the plate-type printing ink according to any one of claims 1 to 3 on a substrate, heat-treating the ink, and curing the ink. The method of forming the sensor.  5. A process formed by the method according to claim 4.  6. A display device, comprising the spacer according to claim 5.